JPS60151218A - Crystalline silicophosphoaluminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention is directed to a novel synthetic crystalline silicophosphoaluminate (=MCM-9'') containing aluminum, silicon and phosphorus in its framework structure. silicophosp
(hoalurni-natg) molecular sieve materials and their use in catalytic conversion reactions of organic compounds. The crystalline material of the present invention exhibits ion exchange properties and can be easily converted into a catalytically active material.

BACKGROUND OF THE INVENTION Zeolite materials, both natural and synthetic, have been shown to have catalytic properties for various types of hydrocarbon conversion reactions. Certain zeolite materials are ordered, with a well-defined crystal structure, identified by X-ray diffraction, in which there are many small cavities interconnected by many smaller pore channels or pores.
It is a porous crystalline aluminosilicate. Within each particular zeolite, these cavities and pores are uniform in size. Because the dimensions of these pores admit adsorbed molecules of a certain size while rejecting molecules of larger size, these materials became known as “molecular sieves,” and these properties can be applied to Molecular sieves, which are utilized in a variety of ways, include a wide variety of cation-containing crystalline aluminosilicates, both natural and synthetic. , in which the tetrahedrons are crosslinked by sharing oxygen atoms, and the ratio of the total number of (aluminum silicon) atoms to oxygen atoms is 1:2.
and Alto, can be described as a strong three-dimensional (reticular) framework structure. The ionic valence of the aluminum-containing tetrahedron is cationic, e.g. alkali metal or 7/
l/, rJ Balanced depending on the presence of IJ earth metal cations within the crystal. This can be demonstrated by comparing aluminum with various cations such as Ca72, Sr/2, Na, K, and LicD (D ratio kc, etc. 1., A). Using these techniques, it is possible to completely or partially exchange cations with other types of cations. Depending on the means of cation exchange, if the cations are selected appropriately, a given cation can be exchanged. It is possible to change the properties of aluminosilicate.

In the dehydration curve, the spaces between the tetrahedra are occupied by water molecules.

A wide variety of synthetic zeolites have been formed by prior art methods. Zeolites include Zeolite A (U.S. Pat. No. 2,882,243), Zeolite X (U.S. Pat. No. 2,882,244), Zeolite Y (U.S. Pat. No. 3)
, 130,007), zeolite zx-sc U.S. Pat. No. 3,247,195), zeolite ZK-4 <U.S. Pat. No. 3,314,752), zeolite ZSM-5
C U.S. Pat. No. 3,702,886), Zeolite ZS
M-LIC U.S. Pat. No. 3.709,979 Iolite ZSM-12 (U.S. Pat. No. 3.832,449);
Zeolite ZSM-20 (U.S. Patent No. 3,972,98
No. 3), Zeolite ZSM-35 <U.S. Patent No. 4.01
6.245), Zeolite ZSM-38 (U.S. Pat. No. 4,046,859), and Zeolite ZSM-23
(U.S. Pat. No. 4,076,842), to name a few, may be named by letters or convenient symbols.

The silicophosphoaluminate of the present invention is not an aluminosilicate zeolite, but it is a molecular sieve material with an ordered pore structure that admits certain molecules while rejecting others.

Aluminum phosphate is described in US Pat. No. 4,310,44, for example.
No. 0 and No. 4.385.994. Aluminum phosphate materials have an electrically neutral lattice and are therefore not effective as ion exchangers or as catalyst components. U.S. Pat. No. 3,801,704 teaches aluminum phosphate treated in a manner to impart acidity.

Canadian Patent No. 911.416: The phosphorus-substituted zeolites of Canadian Patent No. 911.417 and No. 911.418 are “alwminosilicophosphates”.
It is known that some of the phosphorus in it is occluded and is not structural.

U.S. Pat. No. 4,363,748 discloses that silica and aluminum phosphate-calcium-cerium
m-ca L cium-cerium phos
phate) combination is described as a low acid activity catalyst for oxidative dehydrogenation. British Patent No. 168.253 discloses that silica and aluminum phosphate-calcium-tungsten (aluminum-catcium-tungsten)
The combination with 10 p-osph-atg) is disclosed as a low acid activity catalyst for oxidative dehydrogenation. U.S. Pat. No. 4.22 S, O 36 teaches an alumina-aluminum phosphate-silica matrix as an amorphous body mixed with zeolite for use as a cracking catalyst. U.S. Pat. No. 3,213,035 teaches hardness improvement of aluminosilicate catalysts by treatment with phosphoric acid. This catalyst is amorphous.

U.S. Pat. No. 2,876,266 discloses an amorphous active silicophosphoric acid prepared by absorption of phosphoric acid by a preformed silicate or aluminosilicate.
ophosph-oric acid) or salt phase.

Aluminum phosphate is disclosed in US Pat. No. 4,365,095:
No. 4,361,705; No. 4,222.896; No. 4,210゜560: No. 4,179,358: No. 4
, No. 158,621; No. 4.071,471; No. 4,
No. 014,945, No. 3,904,550, they are used as catalyst supports or MJ luxes. The crystalline silicophosphoaluminate thus synthesized has a molecular sieve framework structure with ion exchange properties and is easily and conveniently converted into a material with inherent catalytic activity.

<Characteristics of the present invention> The present invention utilizes aluminum, hereinafter referred to as "MCA1-9",
Synthetic crystalline silicophospoaluminate molecular sieve materials containing silicon and phosphorus and organic,
For example, it relates to its use as a catalyst component in catalytic conversion reactions of hydrocarbons and compounds.

Anhydrous crystalline MCM-9 has the general formula: %Formula% [where M is a cation with a valence of m, and N is a cation with a valence of n
is an anion, and X and 1 are less than -1 and less than +1, and (1) If z is 0, then V is not 0, and (2)
If v is 0, 2 is not 0, and (3) z + y
is a number that satisfies the following relationships: greater than 0.01 and less than l.

In the above composition, when X is greater than V, the silicophosphoaluminate is a cation exchanger with potential use as an acidic catalyst. When X is less than V, the silicophospoaluminate is an anion exchanger with potential use as a basic catalyst. The MCM-9 crystalline material, in its calcined form, has a unique X-ray diffraction pattern as shown in unwritten 1t-B.

As-synthesized MCM-9 ('as-synthesized' may also contain synthetic organic materials, A1 and water molecules. Therefore, it has the general formula: The number of moles of adsorbed organic material, A, arising from the organic directing agent or solvent used and filling the microporosity of MCM-9, which can be removed by calcination, W is, for example, from 0 to about 0, and has a characteristic X-ray diffraction pattern as shown in unwritten fil-A.

The crystalline silicophosphoaluminate of the present invention is a unique material that exhibits a combination of catalytic, adsorption, and ion exchange properties that distinguish it from low-grade aluminum phosphates.

The silicophosphoaluminate materials of the present invention have unique and useful catalytic, adsorption, and Showing shape selection properties. It is well known that aluminum phosphate exhibits a phosphorus/aluminum atomic ratio of only 0.8 to 1.2 and contains no silicon. Also, phosphorus-substituted zeolite compositions, sometimes called "aluminosilicophosphate zeolite 1", are
．． It has a silicon/aluminum atomic ratio of 66 to 8.0 and a phosphorus/aluminum atomic ratio of 0 to 1.0.

The original cations of the as-synthesized MCM-9 can be replaced, at least in part, by ion exchange with other ions, by methods well known to those skilled in the art. Preferred substituted cations include metal ions, hydrogen ions, hydrogen precursors such as ammonium ions, and mixtures thereof. Particularly preferred cations are those that render MCM-9 catalytically active, particularly with respect to hydrocarbon conversion reactions. These include hydrogen, rare earth metals, Groups 1A, 1IA, 11IA, 1VAi, 1B, and n of the periodic table of elements.
Included are Group B, Group ⅠB, Group 1VB and Group Ⅰ metals.

A typical ion exchange method is to contact synthetic MCM-9 with a salt of one or more desired substituted cations. Examples of such salts include halides such as chlorides, nitrates and sulfates.

The morphology of the framework structure of MCM-9, which contains silicon, phosphorus, and aluminum with tetrahedrally coordinated structural positions, is similar to the synthetic aluminum phosphate described in US Pat. No. 4,310,440.

The crystalline MCM-9 of the present invention can be effectively heat treated either before or after ionic father exchange. This heat treatment is carried out by heating the silicophosphoaluminate at a temperature of about 300° C. to about 1100° C., preferably about 35
It is carried out by heating to a temperature of 0° C. to about 750° C. for a period of about 1 hour to about 20 hours. Although reduced pressure or increased pressure can be used for this heat treatment, normal pressure is preferred from the point of view of convenience.

MCM-9 has a distinct X that distinguishes it from other crystalline materials.
The line diffraction pattern is shown. Synthesized MCM-9 X
The line diffraction pattern has distinct values: Table 1-A 16.41±1,2 vs l 0.84±0.1w 9.33±0.1w 8.20±0.1 ””6. 68±0.05 ” 6.17±0.05 w 5.65±U, U 5 ” 5.46±0.05 ” 4.74±0.05 w 4.34±0.05 ” 4.21 ±0.05 ” 4.10±0.03 m 4.05±0.03 m 4.0010, U 3 w 3.94±0.03 m 3.83±0.03 Regular 3.77± 0.03 W 3.64±0.03 w 3.59±0.02 ” 3.39±0.02? l17 3.28±0.02 m 3.16±0.02 w 3.09±0.02 11) 3.03±0.02 v 2.95±0.02 11) 2.90±0.02 w 2.74±0.02 w 2.63±0.02 w Table 1-B shows the results of calcination of MCM-9 (450°C in nitrogen, normal pressure,
The characteristic diffraction lines of MCM-9 in the form of 4 hours) are shown.

Table 1-B 16.36±0. lO love 14.05±0.10” 10.92±0.10w 8.94±0.10 information 8.19±0.10t.

6.90±o, us tc+ 5.50±0.05 m 4.47±0.05 w 4.36±0.05 w 4.08±0.05 vs 3.94±(LO5m 3.79 ±0.05 Dai 3.54±0.03 w 3.45±0.03 w 3.33±0.03 w 3.28±0.02 w 3.22±0.U 2 1D 3.01± 0.02 m 2.95±U, (12w 2.82±0.02 w 2.74±0.02 11) These X-ray diffraction data were obtained using α-irradiation for copper;
Rigaku<R4ctαku) was collected using an X-ray system. The positions of the peaks in 2θ0 (θ is Bragg's angle) were measured by step scanning at 20 intervals of 0.02° and a needle side time of 1 second at each step. Grids measured in Angstroms (4) The spacing, d, and the relative strength of the line after subtracting the background, 1/Io (where io is the strength of the strongest line) were derived using the profile-fitting method.The relative strength is given by the symbol v8- Extremely strong (7
5-100%), 8=strong (50-74%), m=moderate (25-49%) and W-weak (0-24X). It should be understood that this X-ray diffraction pattern is unique to all types of MCM-9 compositions synthesized in accordance with the present invention. Ion exchange of the cations of the silicophosphoaluminate with other ions gives essentially the same X-ray diffraction pattern with some slight shifts in lattice spacing and changes in relative intensity. Other slight variations may occur depending on the silicon/aluminum and phosphorus/aluminum ratios and degree of thermal history of the particular sample.

The crystalline 110M-9 material of the present invention can be converted into a dry, hydrogenated material by the heat treatment described above, either in the organic cation-containing type or in the hydrogen ion precursor type obtained from ion exchange.

In general, the silicophosphoaluminates of the present invention are prepared from a two-phase reaction mixture comprising aluminum, phosphorus and silicon and an organic directing agent(s) and a substantially water-immiscible organic solvent. I can do it. The overall molar composition of the two-phase synthesis mixture in terms of oxide and organic components is as follows.

Cl:CMtO)b:CAl4tOs)e:<5iO
z) d: <ll0s) e: (solvent) f: (anion source) g: (&) However, α/(c+d×g) is smaller than 4, blCe+d+g is smaller than 2, and d/
Cc0g) is less than 2, and f/(c+d+II)
is from 0.1 to 15, g/(c+d+g) is less than 2, and h/(c+d+g) is from 3 to 150. "Solvent" is an organic solvent and "A" is an organic compound or substance derived from an organic directing agent or an organic solvent. The anion is not necessarily added separately to the two-phase system, but other may appear in the product crystals from one or more of the component sources;
Or maybe not.

The reaction conditions are: at a rate of 5°C to 200°C per hour to a temperature of about 80°C to about 300°C, and then at that temperature for about 5 hours to about 500 hours until crystals of MCM-9 are formed. ,
It consists of carefully heating the aforementioned reaction mixture. A more preferred temperature range is from about 100°C to about 200°C, and the time at that temperature range is from about 24 hours to about 168 hours.
It's time.

While heating the reaction mixture and holding it at the desired temperature, p
H must be carefully controlled from about 2 to about 9.

Control of pH can be achieved by adjusting the concentration of added organic and/or inorganic base.

The reaction is carried out until the desired MCM-9 crystals are formed. Is the crystalline product entirely at room temperature? Discard, filter,
By washing with water before drying, the same is separated from the reaction medium and recovered.

The above reaction mixture composition can be prepared using materials that provide the appropriate components. The aqueous phase components can include elements not included in the organic phase, such as from the origins of the elements silicon, phosphorus, or aluminum. The organic phase contains an organic solvent and at least one source of the elements silicon, phosphorus or aluminum which is insoluble in the aqueous phase under the reaction conditions. The aqueous phase also contains the necessary organic and/or inorganic directing agents.

As a non-limiting example, useful sources of aluminum include:
Known forms of aluminum oxide or hydroxide, organic or inorganic salts or compounds are included. Useful sources of silicon include, by way of non-limiting example, known forms of silicon dioxide or organic derivatives including silicic acid, alkoxy- or other compounds of silicon. Organic solvent is G5
Cro alcohol It, M”X- or (E BM+
R'M" ft s) Xt [however,)7 or R'
is alkyl of 1 to 20 carbon atoms, heteroalkyl of 1 to 20 carbon atoms, aryl, heteroaryl, cycloalkyl of 3 to 6 carbon atoms, cycloheteroalkyl of 3 to 6 carbon atoms, or a combination thereof: M is a tetracoordinated element (e.g. nitrogen, phosphorous, arsenic, antimony or bismuth) or a heteroatom in a cycloaliphatic, heteroalicyclic or heteroaromatic structure (
and X is an anion (e.g., fluoride, chloride, bromide, iodide, hydroxide, acetate, sulfate, carboxylate, etc.). It can be selected from the group consisting of = .

When M is a heteroatom in a cycloaliphatic, heteroalicyclic, or heteroaromatic structure, such a structure may include, by way of non-limiting example,
(However, R' is alkyl of 1 to 201 m1 carbon atoms, heteroalkyl of 1 to 20 carbon atoms, aryl, heteroaryl, cycloalkyl of 3 to 6 carbon atoms, or cycloalkyl of 3 to 6 carbon atoms) cycloheteroalkyl].

Particularly preferred directing agents for the process of the invention are onium as defined above, wherein R is 1 to 4 carbon atoms, M is nitrogen, and X is a halide or hydroxide. Compounds are included. Non-limiting examples of these include tetrapropylammonium hydroxide, tetraethylammonium hydroxide and tetrapropylammonium bromide.

Inorganic hydroxides or salts of suitable composition can also be used as supplementary directing agents, non-limiting examples include (:sO
H%KOR, CsC1%KCl and similar.

MCM-9 crystals produced according to the present invention can be formed into a wide variety of particle sizes. Generally speaking, the particles are powders, granules, or extruded articles having a particle size that passes through a 2-mesh (Tyler) sieve well and remains on a 400-mesh (Tyler) sieve. It can be made into a form. When the catalyst is molded, for example, by extrusion molding, the catalyst can be extruded before being dried, or it can be partially dried and then extruded.

It would be desirable to composite the new MCM-9 crystals with other materials or matrices that are resistant to the temperatures and other conditions used in organic conversion processes. Such materials include active and inert materials and threatening or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter may be of natural origin or in the form of a gel-like precipitate, or a gel containing a mixture of silica and metal oxides. M
Catalyst compositions containing CM-9 crystals generally range from about 1 to 9
0% by weight MCM-9 material and from about 10% to 99% by weight MCM-9 material. More particularly, such catalysts contain about 2 to 80% by weight of the new MUM-9 and about 2 to 80% by weight.
0 to 98% by weight of IJ Lux.

The use of active materials in combination with the novel MCM-9 crystals tends to alter the overall conversion and/or selectivity of the catalyst in certain multi-conversion processes. Inert substances serve well as agents to control the amount of conversion in a given reaction, so that the product can be obtained economically and regularly without resorting to other means of controlling the rate of reaction. I can do it. These materials may also be incorporated into naturally occurring clays such as bentonite and kaolin to improve the crush strength of the catalyst under productive operating conditions. The materials, ie clays, oxides, etc., act as binders for the catalyst. Since it is desirable to prevent catalysts from disintegrating into powdered materials for commercial production use, it would be desirable to provide catalysts with good crush strength.

These clay binders are normally used only to improve the crush strength of the overall catalyst.

Naturally occurring clays that can be composited with the new crystals include montmorionite and the kallion family, which includes zabubentonite and kaolin, known as Dixie, McNamee, Jorja and Florida clays, or whose main mineral constituents are halloysite, Includes other minerals that are kaolinite, zitzkite, nacrite, or anauxite.

The clay can be used either in its raw, as-mined state, or in its calcined, acid-treated μP or chemically modified form.

In addition to the aforementioned materials, crystalline MCM-9 may also contain porous matrix materials such as aluminum phosphate, silica-alumina,
Silica-magnesia, silica-zirconia, silica-thoria, silica-beryria, silica-titania and composites with ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia I can do it. The relative proportions of the finely divided crystalline material and the inorganic oxide gel matrix range from about 1 to about 90% by weight of the composite and more usually as a catalyst for the novel MCM-9 materials of the present invention, particularly in the composite. When the active form is used as the catalyst component, the catalyst likely contains additional hydrogenation components, and the reformed feed is heated at a temperature of about 370° C. to about 540° C. and about 100 p.p.
sig to approximately 1000 psig (791 to 6996
kPa), preferably from about 200 pgig to about 70 pgig
A pressure of 0 psjg (1480 to 4928 kPa), from about 0.1 to about 10, preferably from about 0.5 to about 4
liquid hourly space velocity of about 1 to about 20, preferably about 4
Hydrogen/hydrocarbon molar ratios of from to about 12 can be used.

Catalysts comprising MCM-9 materials of the present invention can also be used for the hydroisomerization of n-paraffins when a hydrogenation component such as platinum is provided. Kahero hydrogen isomerization temperature is approximately 90℃
from about 375°C, preferably from about 145°C to about 290°C
io from 0 to about 2, preferably about 0 at a temperature of 'C.
．． It is carried out using a liquid space velocity of 25 to about 0.50 and a hydrogen/hydrocarbon molar ratio of about 1=1 to about 5:1.

Additionally, such catalysts can be used for olefin or aromatic isomerization using temperatures of about 200°C to about 480°C.

Such a catalyst can also be used to lower the pour point of light oil. The reaction is conducted at a liquid hourly space velocity of about 10 to about 30 and a temperature of about 425°C to about 595°C.

Other reactions that can be accomplished using the MCM-9 catalyst of the present invention containing metals such as platinum include hydrogenation-dehydrogenation and desulfurization reactions, olefin polymerization (oligomerization) and other organic compound reactions. Conversion reactions, such as alcohols (e.g. methanol) or ethers (
Examples include the conversion of dimethyl ether) to hydrocarbons, and the alkylation of aromatics in the presence of an alkylating agent (eg ethylene).

In order to more fully illustrate the nature of the invention and the manner in which it may be carried out, the following examples are presented.

EXAMPLE When collecting adsorption data in order to compare the adsorption capacities of various adsorbents, it was done as follows.

monohexane, 2-methylpentane, xylene or cyclohexane vapor. For adsorbates other than O-xylene and water, the sample temperature was maintained at 90°C. The temperature was 120°C for O-xylene and 60°C for water. The weight gain was determined gravimetrically and converted to adsorption capacity of the sample as weight percent of calcined adsorbent.

When alpha values are tested, the alpha value is a rough measure of the catalytic cracking activity of the catalyst compared to a standard catalyst, and the alpha value is the relative rate constant (per unit time).
Note that n-hexane conversion rate per volume of catalyst) is shown. The activity of the highly active silica-alumina decomposition catalyst is expressed as l of alpha (Kokuho constant = 0.0165ec-')
This is the standard for me. In the case of zeolite) nzsyL5, only 174
No ppm of tetrahedrally coordinated AI or OsL was required. The alpha test is based on U.S. Patent No. 885407
No. 8 and The Journal of Cataris (i'he
Journ, al of Cata 17tsis, Volume 4, Pages 522-529 (August 1965).

When testing ion exchange capacity, the temperature of the ammonium form of the silicophosphoaluminate is determined by titration with a solution of ammoniacal sulfamic acid generated during programmed decomposition. This method was developed by G.T.Kr (G, T, Kgrr) and Nie.
W Chester (A, W, Chester)
Thermostain Force Acta CThermoc 1m
1ca Acta) Volume 8, pp. 118-124 (19
1971).

Example 1 Organic phase consisting of Si (OCt Hs ) 4 10 & and 1-hexanol 60.9 and Bs 7'04
(s 5%) 2 B-1g-A120s13.7.1
i+1 G-n-propyl amide/10.1. ! i' and H
20's '59.6. A two-phase reaction mixture was prepared using an aqueous phase consisting of F.

The reaction mixture as a whole was atomically 9.3% Si13
It had a composition containing 8.8 SP and 51.9% Al. The directing agent was di-n-propylamine. 73H at the start was between 5 and 7.

The reaction mixture was heated to 180°C Gc at 50°C/hr and held at that temperature for 24 hours. It was then heated to 200° C. and held at that temperature for 24 hours until crystals of silicophosphoaluminate formed.

The crystalline product was separated from the reaction mixture by 1:I filtration, washed with water and dried at 80°C. Analysis of the product crystals revealed 13, 1-Si, 42.7% P and 44.2% A.
It contained 1 atoms. When a sample of freshly synthesized silicophosphoaluminate was subjected to Xm analysis, Table 2
It was revealed that it has a molecular sheep structure with the diffraction lines shown in .

Table 2 2.6188 84.218 8. is Example 2 The synthesis of Example 1 was repeated, keeping the reaction mixture at 200° C. for 48 hours. Crystalline silicophosphoaluminate has 14.5% Sj, 42.4% P and 43.1% A in atoms
Analysis revealed that it contains l. When a sample of the freshly synthesized silicophosphoaluminate was subjected to X-ray analysis, it was found to have a molecular sheep structure exhibiting the diffraction lines shown in Table 8.

Table 8 10・8449 8.146 7.499・8882
9.468 14.692.6278 84.097
6.96 Example 8 A portion of the crystalline silicophosphoaluminate of Example 2 was calcined in nitrogen at 450° C. for 4 hours and then subjected to X-ray analysis.

The results are shown in Table 4.

Table 4 Examples A portion of the crystalline silicophosphoaluminate of Example 1 was calcined in the manner described in Example 3 and I M NH4N
Ammonium exchange was performed using Us solvate. The ion exchange capacity added from the generation of ammonia is 0.22 me
It was determined to be q/g.

Examples & The ion conversion capacity of the crystalline silicophosphoaluminate of Example 2 was determined as described in Example 4. That is 0.105
It was meq/9.

EXAMPLE A portion of the crystalline silicophosphoaluminate of Example 5 was calibrated using the alpha test. Its alpha value was 1.4.

Example 7 A part of the crystalline silicophosphoaluminate of Example 5 was converted into (
No. 4,885,195, incorporated herein by reference)
1ndex) was used to conduct the test. Constraint coefficient is 0
．． 4, indicating the presence of large pores.

Example 8 A sample of the crystalline silicophosphoaluminate calcination product of Example 1 was evaluated for adsorption properties to confirm its molecular sheep properties. The results presented in the case study were as follows: Water (60°C): 1.78 n-Hexane (90°C): 1. OO Example 9 A sample of the calcined product of Example 2 was also evaluated for adsorption properties. Heavy lf1. The results, expressed in %, were as follows: water (
60°C): 8.8 n-hexane (90°C>: 1.1

Claims (1)

[Claims] L Silicon, phosphorus, and aluminum whose X-ray diffraction pattern measured as synthesized exhibits the characteristic X-ray diffraction pattern shown in Table 1-A of the present specification. Synthetic crystalline substances containing. 2. A synthetic crystalline material according to claim 1, whose X-ray diffraction pattern measured on calcination shows the characteristic X-ray diffraction pattern shown in Table 1-B of this specification. a Following formula: % formula %: 0 (However, M is a kanaon with valence m, and N is valence n
is the anion of , A is the organic directing agent, τ is the number of moles of A, W is the number of moles of H, O, and 2 and V are greater than -1 and less than +1, and ( 1) If z is O, then V is not 0, (2) If v is 0, then X is not 0, and (3) z+y is 0.
．． 001, and is less than 1.
Synthetic crystalline substances as described in Section. 4 In an anhydrous state, the following formula: % formula % [However, M is a cation with a valence of m, and N is a cation with a valence of n
is an anion, and X and y are greater than -l and +1
and (1) if z is 0, y is not 0, (2) if y is 0, then X is not 0, and (3) z + y is 0.
．． 001 and less than 1]
Synthetic crystalline substances as described in Section. & The cation of υ is at least partially hydrogen and hydrogen precursors, rare earth metals,
Substitution with at least one cation selected from the group consisting of Group 1A, Group mA, Group 11'A, Group 1B, Group nB, Group ME, Group NB, and first layer metals. A crystalline material according to any one of claims 1 to 4. A synthetic crystalline material containing silicon, phosphorus, and aluminum, characterized in that an X-ray diffraction pattern measured as-synthesized exhibits a characteristic X-ray diffraction pattern shown in Table 1-A herein. at least a portion of the initial cation of hydrogen and hydrogen precursors, rare earth metals and the first periodic ensemble of elements.
At least one metal selected from the group consisting of Group A, Group ■A, Group 111 A, Group ■A, Group 1B, Group 11B, Group mB, Group NB, and the first layer metal. A crystalline substance obtained by substitution using a cation and heat treatment. 7. A synthetic crystalline material containing silicon, phosphorus, and aluminum, characterized in that an X-ray diffraction pattern measured as-synthesized shows a unique X-ray diffraction pattern shown in Table 1-A of the present specification. A catalyst consisting of & The catalyst according to claim 7, which is used for converting organic compounds.